Printing composition and process



Patented Feb. 9, 1937 UNITED STATES PRINTING .COMPOSITION AND PROCESS Ivan F. Chambers, Wilmington, Del., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application May 9, 1934, Serial 19 Claims.

This invention relates to the art of printing,

and more particularly to methods of printing lustrous artificial cellulosic fabrics whereby unusual efiects are obtained.

Oneof the objects of the invention is the provision of new and improved printing pastes suitable for printing artificial cellulosic fabrics whereby new and unusual color effects may be obtained. Another object is the provision of printing pastes of the character above described which are suitable for application to cellulose acetate. A further object is to produce differential lusters or damask effects without recourse to elaborate weaving processes. A still further object is to produce relatively permanent subdued color effects which will withstand ordinary laundering. An additional object is to produce color effects of the character above described without rendering the fabric stiff or harsh to the hand 20 and without injuring the original draping properties of the fabric. Other objects will appear hereinafter.

These objects are accomplished by printing lustrous artificial cellulosic fabrics with printing pastes containing water-insoluble organic pigments having a cyclic chemical structure, preferably ethylene-glycol-di-beta-naphthyl-ether.

Many variations are permissible in carrying out the invention, any one or all of which leave 0 30 a desired effect upon the results obtained. The lustrous artificial cellulosic fabric may be dyed or undyed when subjectedto the printing process. If a white, undyed fabric is employed with a white printing paste such asjfor example, an intimate mixture of a suspension of ethylene-glycol-dibeta-naphthyl-ether, a swelling agent and a thickener, beautiful white damask effects may be obtained by printing from an engraved printing roll. If a dyed fabric is similarly treated, new and unusual subdued color effects are obtained.

The process may also be carried out by incorporating a suitable dye into the printing paste together with the water-insoluble organic pigment and other customary ingredients. In this way, different color effectsmay be obtained. Still other color effects may be obtained by first printing the fabric with the white printing paste and then dyeing it. P Instead of applying the printing paste from engraved or embossed rolls, stencils, etc., it may be applied in what is known as a blotch roll, which produces a uniform delustering over thedyed surface of the fabric.

Although not essential to the process, improved results are obtained by the incorporation into the printing paste of substances-which have the property of swelling theartificial cellulose fiber.

- As examples of substances which have given especially desirable results in certain instances may be mentioned diethylene glycol, sodium mmcyanate, ammonium thiocyanate, diethylene glycol-monoethyl ether and organic thiocyanates such as, for example, guanadine thiocyanate. Such substances are particularly desirable for use in the treatment of cellulose acetate fibers.

The results obtained are greatly affected by the size of the water-insoluble organic pigment particle. The desired particle size is usually obtained by grinding an aqueous suspension of the organic pigment in a colloid mill with a suitable dispersing agent or protective colloid, preferably an alkali metal caseinate, such as sodium caseinate. For the purposes'indicated in this invention, the organic pigment dispersion should preferably be ground until a particle size of from 2 to 4 microns is obtained. A smaller particle size may be employed.

In order to produce effects of the character described on cellulose acetate with ethylene-glycol-di-beta-naphthyl-ether, the following general procedure may be employed:'

A fine suspension of ethylene-glycol-di-betanaphthyl-ether is prepared by grinding the following mixture in a colloid mill:

25.0 parts ethylene-glycol-di-beta-naphthylether crystals 0.5 parts sodium caseinate 74.5 parts water The above mixture is recirculated in the mill until a particle size of 2 to '4 microns is obtained.

' After grinding is. completed, a non-settling suspension of ethylene-glycol-di-beta-naphthylether is obtained which may be employedin various concentrations in printing pastes, dependent upon the results desired. Suitable printing pastes may contain from 10% to 40% of ethylene-glycoldi-beta-naphthyl-ether suspension, 0% to of a swelling agent such as diethylene glycol or diethylene glycol-monoethyl ether and the remainder a neutral thickening agent such as a 6% solution of gum tragacanth. The printing paste is applied as previously described.

After application of the printing paste, the material is dried and steamed for a suitable length of ,time. If swelling agents are employed in the printing paste, adsorption and fixation of the pigment is obtained in a shorter length of time than without the addition of these assistants. In general, excellent fixation is obtained by five-minutes steaming or ageing in a continuous ager if 20 of diethylene-glycol or diethylene glycol-monethyl ether is employed in the printing paste. If no swelling agent is used, a steaming for twenty to thirty minutes is normally required. The delustered material is suitable for certain purposes immediately after steaming. For other purposes, it is advisable to soap the material for five minutes in a 0.5% soap solution in order to remove unfixed particles, gum, etc.

The invention will be further illustrated, but

is not limited, by the following examples, in

which the parts are by weight.

Example I A printing paste was prepared as follows:

40 parts ethylene-glycol-di beta naphthylether (25% suspension dispersed with sodium caseinate as previously described) were mixed with 40 parts of a 6% gum tragacanth solution.

20 parts diethylene glycol were then added Example II The following printing paste was prepared:

30 parts of ethylene-glycol-di-beta-naphthylether as employed in Example I were mixed with 70 parts of a 6% gum tragacanth produce a smooth paste.

solution to Cellulose acetate piece-goods were printed with the above printing paste. and the printed material dried. The printed material was then steamed for thirty minutes in a Cottage steamer. After steaming, the goods were rinsed in cold water, soaped-for five minutes in a 0.5% soap solution at 160 F., again rinsed, and dried.

A dull luster was obtained on the fabric according to the pattern of the printing roll, forming a damask eiiect as in Example I.

Example III The same printing paste and printing procedure was employed as in Example I. In this example, however, a blotch printing roll was used to apply the printing paste which resulted in a uniform delustered efiect which covered the entire surface of the material.

' I Example IV A printing paste was prepared as follows:

20 parts of ethylene-glycol-di-beta-naphthylether suspension as employed in Example I were mixed with 20 parts of diethyleneglycolmonoethylether, and added to 60 parts of a 6% gum tragacanth solution The whole was then stirred to form a smooth paste. Cellulose acetate piece-goods were printed with the above printing paste, dried, and aged for six minutes in a Mather Platt ager at 216 F.

' After ageing, the material was rinsed in cold water and dried. The printed material was de lustered according to the pattern of the printing roll, producing a damask 'efiect.

Example V Cellulose acetate material which was printed as in Example I was dyed with SRA Orange I (4- nitrobenzene-azodiphenylamine), a dispersed type of dyestufi suitable 'for cellulose acetate fibers, according to the following procedure:

A dye-bath .was prepared containing:

0.3 part SRA Orange I 1.5 parts soap 298.2 parts water The dye-bath was heated to F after which a five part swatch of cellulose acetate delustered according to Example I was. entered and dyeing continued for thirty minutes. The material was then rinsed in cold water and dried. The delustered portions of the fabric were dyed a lighter shade than the lustrous portions.

Example VI A printing paste was prepared as follows:

1 partof SRA Orange I (4-nitr6benzene-azodiphenylamine)-was mixed. with 59 parts of a 6% gum tragacanth solution, to

which were added 40 parts of ethylene-glycol-di-beta-naphthylether suspension as employed in Example I.

and the whole well-stirred to form a smoothpaste.

Cellulose acetate piece-goods were printed with the above printing paste, dried and steamed for one hour in the Cottage steamer. After steaming, the material was rinsed in cold water and soaped for fiveminutes at F. in a 0.5% soap solution,

rinsed in cold water, and dried. A dyed as well as delustered efiect was obtained according to the pattern.

7 Example VII A printing paste was prepared as follows:

2.5 parts of commercial 6:6'-diethoxy-thioindigo paste were mixed with 30.0 parts of ethylene-glycol-di-beta-naphthyl-ether suspension as employed in Example I, to which-were added 20.0 parts of diethylene glycol. After mixing f thoroughly 47 .5 parts of 'I'hickener A were added.

The5 whole was then stirred to produce a smooth pas e. 1

Thickener A 75 parts of 'Thickener B were heated to F. and 8 parts of potassium carbonate added. This ingredients added:

6 parts of Sulfoxite C (sodium sulfoxylateformaldehyde) 5 parts of glycerin 6 parts of water was cooled to 140 F., and the following Thickener B 10 parts wheat starch and 30 parts British gum were added to 60 parts water ten minutes and cooled, producing a smooth paste.

Cellulose acetate piece-goods were printed with the above printing paste, dried and aged for five minutes at 216 F. in a vat color ager of the Mather Platt type. The printed material was then treated in an oxidizing bath at 160 F. containing 0.5% sodium bichromate and 0.5% acetic acid (glacial). The material was then rinsed, soaped for three minutes in a soap-bath at 160 F. containing 0.5% soap, again rinsed, and dried.

An orange colored delustered effect was obtained according to the pattern of the printing roll.

While in the foregoing examples ethyleneg1ycoldi-betanaphthal-ether is the organic pigment employed and this substance has given especially desirable results, it will be understood that other light-colored organic substances of the class described having similar properties may be employed.

As examples of substances which may be used instead of ethylene-glycol-di-beta-naphthylether may be mentioned: di-beta-naphthyl-sulfide, beta-naphthyl-thienyl-ether, dithienyl-ether of para:para'-dihydroxy-diphenyl, di-biphenylether, 'di-beta-naphthyl-ether, dibenzyl-ether of symmetrical -hydroxy-di-beta-naphthyl-ether, symmetrical 5-chloro-di-beta-naphthyl-ether; alpha-naphthyl-methyl-beta-naphthyl-ether, symmetrical 5 methoxy-di beta-naphthyl ether; difurfuryl-ether of ethylene glycol, di-betanaphthyl-mercapto-ethyl-sulfide, dibenzthiazylmercapto ethane, beta-naphthoxy-ethyl-betanaphthyl-sulfide, 1 :2-di- (beta naphthyl mercapto)-ethane, dicarbostyril-ether of ethylene glycol, di-alpha-naphtyl-ether of ethylene glycol (M. P. 127.5 C.), di-beta-naphthy'l-ether of diethylene glycol (M. P. 122 C.) di-beta-naphthylether of trimethylene glycol (M. P. 147 C.), dibeta-naphthyl-ether of propylene glycol (M. P. 152 0.), di-beta-naphthyl-ether of dipropylene glycol (M. P. 136 C.), ethylidene-di-beta-naphthyl-ether, dinaphthyl-ether of triethylene glycol, di-naphthyl-ether of tripropylene glycol, 1:3-dibeta-naphthyl-ether of glycerin, di-beta-naphthyl-ether of glycerin chlorohydrin, tri-betanaphthyl-ether of glycerin, di-beta-naphthylether of beta-monoethylin, di-beta-naphthylether of 1:4-cyclohexanediol, beta-naphthoxyethyl-beta-naphthyl-ether of 1:4-cyclohexanediol, beta-naphthoxy-ethyl-beta-naphthyl-ether of glycerin, di-(5-chloro-alpha-naphthyl) -ether of ethylene glycol, 1zfi-dibromo-beta-naphthylether of ethylene glycol, beta-naphthyl-thienylether of ethylene glycol, ethyl-phenyl-naphthylether of glycerol, tetrabenzyl-ether of sorbitol, tribenzyl-ether of glycerin, tetrabenzyl-ether of pentaerythritol, beta-naphthyl-benzyl-ether of ethylene glycol, di-biphenyl-ether of glycol; 1:4- di naphthoxy butene 2, i 4 di-naphthoxy-2- methylbutene-2, 1 :4-dinaphthoxy-2-chlor butene-2, tetrahydro-naphthyl ether of ethylene glycol, diphenyl-ether of ethylene glycol, diphenyl-ether of glycerin, diphenyl-naphthoxyethanol; ether resins from diphenylol-propane and dichloro-diethyl-ether, diphenolol-sulfone and dichloro diethyl ether, tetrachloro di The above mixture was heated at the boil for water-insoluble and are adsorbed by artificial cellulose in the presence of steam. They are usually much softer and have refractive indexes differ'ent from those of commonly used inorganic 1 pigments such as zinc oxide (2.0) and titanium dioxide (2.5+). Most organic compounds have more than one refractive index. Typical exampics are the following in which the lowest principal index is 1.62 or lower: ethylene-glycol-dibeta-naphthyl-ether (3 principal indexes: 1.55, 1.68 and approximately 1.80), diethylene-glycoldi-beta-naphthyl-ether (3 principal indexes: 1.54, 1.68 and approximately 1.80), 1: 3-di-beta-naph thyl-etherof glycerin (at least 2 principal indexes: approximately 1.62 and 1.67), symmetrical dibenzthiazyl-mercapto-ethane (at least 2 principal indexes: one approximately 1.50 and the other above 1.78).

The following comparative tests illustrate the advantages of organic pigments suchas ethyleneglycol-di-beta naphthyl ether over inorganic pigments such as zinc oxide under similar methods of application. Four printing pastes were prepared, two containing ethylene-glycol-dibeta-naphthyl-ether and the other two zinc oxide, as follows:

40 parts ethylene-glycol-di-beta-naphthylether (25% suspension) 3 parts diethylene glycol 40 parts gum tragacanth (6% solution) 40 parts ethylene-glycol-di-beta-naphthylether suspension) 10 parts water 50 parts gum tragacanth (6% solution) 10 parts zinc oxide 20 parts diethylene glycol parts water parts gum tragacanth (6% solution) 10 parts zinc oxide 40 parts water parts gum tragacanth (6% solution) Swatches from the above prints were given an additional soaping of ten minutes at 140 F. in a 0.5% soap solution, rinsed, and dried. The

following comparisons were made:

I Comparison between prints (1) and (3) (Diethylene glycol employed as a swelling agent with equivalent quantities of pigment.)

One minute scoping-120 F.Print (1) was approximately ten times stronger than print (3).

Ten minute scoping-140 F.Print (1) was approximately ten times stronger than print (3).

Comparison between prints (2) and (4) (Equivalent quantities of pigment; no swelling agent employed.)

One minute soaping120 F.Print (2) was approximately fifteen times stronger than print Ten minute scoping-140 F.Print (2) was approximately fifteen times stronger than print In general, the organic pigments are preferably substances of the character described selected from the class of compounds consisting of organic ethers containing closed chains, and

thereof, preferably containing at least three carbocyclic and/or heterocyclic nuclei. Each closed chain is here considered as a nucleus. Thus. naphthalene has two nuclei; carbazole has three nuclei. The nuclei are preferably unsaturated. Hydrogen atoms may be replaced by monovalent radicals such as, for instance, an alkyl group, an alkoxyl group, a hydroxy-alkyl group and/or a halogen atom. Special mention may be made of compounds having the following general formula:

in which A represents an aliphatic hydrocarbon or hydrocarbon ether radical and n represents an integer larger than one.

The cyclic organic ether compounds and analogues thereof employed in accordance with this invention, including those mentioned above,exist as stable solids under the conditions of printing; that is, they are solids at temperatures above 100 C. The term ether linkage is intended to include the simple ether element as well as more complex organic ether radicals such as, for example,

These and many other ether linkages occur in the specific compounds mentioned above. It will be recognized that in the analogues of such ethers herein referred to, one or more of the oxygen atoms are replaced by S-, Se-, Te or NH.

The printing pastes may be prepared, in general, according to the methods previously given in the examples and preceding description. Other types of thickeners ordinarily used in printing pastes may be used. In preparing the dispersion of organic pigment, other dispersing agents such as, for example, alkylnapththalene-sulfonates, soaps, sulfonated oils, and the like may be employed.

Where a reducing agent is necessary as in printing vat dyes, glucose and sodium-formaldehyde-sulfoxylate are especially suitable. Further examples of vat dyes are dimethoxy-dibenzanthrone, 4:4 dimethyl-6 6 dichlorothioindigo, 6:6'- dichloro indigo, :5'- dichloro 7:7'- di methyl-thioindigo, tetrabromo-indigo and monochloro N dihydro 1:2:2':1' anthraquinone azine. Examples of other colors which may be employed are: 1 :4 :5 8-tetra-amino-anthraquinone, 1hydroxy-4chloranthraquinone, demethylated 1 :4-dimethylamino-anthraquinone, 1 :4-diamino-anthraquinone, l-methyl-amino-anthraquinone, 1amino-4-hydroxy-anthraquinone, 1- amino-Z-methyl-anthraquinone, 1:4-dimethyldiamino-anthraquinone, 1 :4-diamino-2-methoxyanthraquinone, methylated 1 :4-diamino-anthraquinone and l-nitro-acridone. In general, any color which is used in printing the artificial cellulose according to ordinary methods may be incorporated into the printing paste. If the fabric is dyed before or after printing, any dye normally used for dyeing such fabrics may be employed.

The artificial cellulose materials which the invention especially contemplates the treatment of are lustrous fabrics made from or containing cellulose acetate or other organic esters of cellulose such as, for example, cellulose formate, propionate or butyrate, or made from or containing cellulose ethers such as methyl, ethyl or benzyl cellulose or the corresponding products of cellulose and glycols or other polyhydric alcohols It is well known that these substances are usually produced in lustrous form and that, for many purposes, such lustrous fabrics are undesirable. The present invention therefore turns this disadvantage into an advantage by enabling the production of differential luster or damask efiects. The usual type of inorganic pigments do not give satisfactory results. Ordinarily, where they have been applied locally, it has been with a binding agent such as nitrocellulose solution or albumen which, when dried, mechanically binds the pigment to the fiber.

Subdued luster effects obtained by the present process do not have a fiat and pigmented appearance which is common with fabrics delustered with metallic pigments. Although the finished fabric may have an extremely matte effect, the

delustering appears to be part of the fiber and not painted on the surface as with other methods. This is probably due to the adsorption of the organic pigment particles by the fiber and, also, to the difference in refractive index between such particles and the inorganic pigments.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that I do not limit myself to the specific embodiments thereof except as defined in the following claims.

I claim:

1. A printing paste comprising dispersed ethylone-glycoldi-beta-naphthyl-ether.

2. A printing paste comprising essentially an intimate mixture of about 10% to about 40% of a- 25%-aqueous suspension of ethylene-glycol-dlbeta-naphthyl-ether having a particle size of about 2 to about 4 microns and containing about 0.5% to about 0.7% sodium caseinate, 0% to about 20% diethylene glycol, and the remainder a hen-- tral, approximately 6% solution of gum traga of cellulose ester and ether materials with a printing paste including finely divided ethylene glycoldi-beta-naphthyl-ether.

4. In a process of producing damask eifects on a cellulose acetate fabric, the step which comprises applying' to a lustrous cellulose acetate fabric from an engraved printing roll a printing paste including finely divided ethylene-glycol-dibeta-naphthyl-ether.

5. In a process of producing damask effects on a cellulose acetate fabric, the step which comprises applying to a lustrous cellulose acetate fabric from an engraved printing roll a printing paste including finely divided ethylene-glycol-dibeta-naphthyl-ether and diethylene glycol.

6. In a process of producing damask effects on a cellulose acetate fabric, the step which comprises applying to a lustrous cellulose acetate fabric from an engraved printing roll a printing paste including finely divided ethylene-glycol-dibeta-naphthyl-ether and a dye for cellulose acetate.

7. In a process of producing damask effects on a cellulose acetate fabric, the step which comprises applying to a lustrous dyed cellulose acetate fabric from an engraved printing roll a printing paste including finely divided ethyleneglycoldi-beta-naphthyl-ether.

8. In a proces of .producing improved delustered effects on artificialfabrics of the cellulose ester and ether type, the step which comprises printing a lustrous fabric selected from the class consisting of cellulose ester and ether materials with a printing paste including a white, water-insoluble cyclic ether containing at least three unsaturated closed chains, of which at least two are connected together by an ether linkage, said ether existing as a solid under the conditions of printing.

9. In a process of producing improved delustered effects on a cellulose ester fabric, the step which comprises printing a lustrous cellulose ester fabric with a printing paste including a dispersion of a white, water-insoluble polynuclear diether of a polyhydric alcohol, said ether containing at least three closed chains and existing as a solid under the conditions of printing.

10. In a process of producing improved delustered effects on cellulose acetate, the step which comprises printing lustrous cellulose acetate with a printing paste including a white, water-insoluble dinaphthyl ether of an aliphatic polyhydric alcohol.

11.- A printing paste comprising a dispersion of a white, water-insoluble organic pigment selected from the class consisting of organic ethers containing more than one closed chain connected by an ether linkage, and -'S--, Se, Te and NH analogues hereof, said ethers and analogues thereof exis ing as solids at temperatures above 100 C. under the conditions of printing.

12. A printing paste comprising a substance which has the property of swelling artificial cellulosic fibers and a dispersion of a white, water-insoluble organic pigment selected from the class consisting of organic ethers containing more than one closed chain connected by an ether linkage, and -S-, Se, 'I'e' and NH analogues thereof, said ethers and analogues thereof existing as solids at temperatures above 100 C. under the conditions of printing.

13. A printing paste comprising a dispersed water-insoluble dye and a dispersion of a white,

water-insoluble organic pigment selected from the class consisting of organic ethers containing more than one closed chain connected by an ether linkage, and S, Se, --Te and NH- analogues thereof, said ethers and analogues.

thereof. existing as solids at temperatures above 100 C. under the conditions of printing.

14. A printing paste comprising a dispersed water-insoluble vat dye. a reducing agent which is adapted to reduce said dye to its leuco derivative on heating, and a dispersion of a white, waterinsoluble organic pigment selected from the class consisting of organic ethers containing more than one closed chain connected by an ether linkage, and S-, Se, -'I'eand NH analogues thereof, said ethers and analogues thereof existing as solids at temperatures above 100 C. under the conditions of printing. I

15. A printing paste comprising an intimate mixture of about 10 to about 40% of an aqueous suspension of a white, water-insoluble dinaphthyl ether of a lower aliphatic polyhydric alcohol having a particle size of about two to about four microns and containing a small amount of a dispersing agent, 0 to 20% diethylene glycol and the remainder thickener.

16. In a process of producing improved delustered effects on artificial fabrics of the cellulose ester and ether types, the step which comprises printing a lustrous fabric selected from the class consisting of cellulose ester and ether materials with a printing paste including a dispersion of a white, water-insoluble compound selected from the class consisting of organic ethers containing at least two closed chains connected by an ether linkage, and --S--, Se, --Te-. and --NH- analogues thereof, said ethers and analogues thereof existing as solids at temperatures above 100 C. under the conditions of printing.

, 1'7. In a process of producing improved delustered effects on cellulose acetate materials, the step which comprises printing on a lustrous cellulose acetate material with a printing paste comprising a dispersing agent, a swelling agent, a thickener and a white, water-insoluble organic ether containing at least four unsaturated closed chains of which at least two are connected together by an ether linkage, said ether existing as a dispersed solid under the conditions of printing and having a particle size of about two to about four microns.

18. Cellulose ester and ether fabrics containing lustrous and non-lustrous areas, said non-lustrous area comprising a compound selected from the class consisting of a white, water-insoluble organic ether containing more than one closed chain connected by an ether linkage, and S, Se,

. Te-- and NH- analogues thereof, said ethers high-melting dinaphthyl ether of a lower aliphatic 'polyhydric alcoholwhich is adsorbed throughout the non-lustrous area.

IVAN F. CHAMBERS. 

